JP2003128725A - Method for manufacturing curable resin and composition containing curable resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a curable resin in which a reaction between an acidic group and an epoxy group during pre-baking is suppressed so that the failure of development is improved, and the generation of residual films during development is suppressed, and to provide a composition containing the curable resin obtained by the method. SOLUTION: The method for manufacturing a curable resin consisting of a modified copolymer (D) is carried out as follows: the modified copolymer (D) is obtained by adding an epoxy-containing unsaturated compound to a part of acidic groups of a copolymer obtained from a (meth)acrylic acid ester (A) and a compound (B) containing an unsaturated group and having at least one acidic group; and the addition reaction is carried out in the presence of a catalyst and its oxide. The curable resin composition contains the curable resin obtained by the method, a photopolymerization initiator, optionally a dilution monomer or oligomer, and optionally an epoxy compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a curable resin and a composition containing the curable resin obtained by the method. More specifically, after the film is formed, the method for producing a curable resin capable of easily forming an image by exposure to light and development with a dilute aqueous alkali solution, and the heat resistance (heat fog resistance) containing the curable resin obtained by the method are improved. The composition. Curable resins and compositions thereof are particularly suitable for printed wiring boards, L related to electronics.
It is useful as a binder resin for resist inks such as SI relations, color filters accompanying liquid crystals, and sealants.

[0002]

2. Description of the Related Art In recent years, due to environmental problems, resource saving, energy saving, workability improvement, etc., in the field of image formation using a photoresist, solvent development has shifted to dilute alkaline aqueous solution development. In the field of printed wiring board processing, the resist ink is shifting from solvent development type to dilute alkaline aqueous solution development for the same reason. In printed wiring boards, solder resist resins are widely used as permanent protective coatings for circuit boards. The solder resist is formed on the entire surface of the base circuit conductor except the portion to be soldered. Its main role is to prevent solder from adhering to unnecessary portions when soldering electronic components to a printed wiring board, and to prevent oxidation and corrosion of circuit conductors. Conventionally,
When forming a solder resist on a printed wiring board, a thermosetting type resist ink was printed by a screen printing method, and the transfer part was thermoset or UV-cured. However, the screen printing method has a problem that bleeding, bleeding, and sagging occur at the time of printing, and it cannot cope with the recent increase in the density of circuit boards. A photographic method was developed to solve this problem. The photographic method is a method of forming a desired pattern by exposing through a film on which a pattern is formed and then developing.

An organic solvent has been conventionally used for developing such a photo solder resist ink. However, in recent years, due to the problem of environmental pollution, there is a tendency to shift to a type capable of developing with a dilute alkaline aqueous solution. Such a resist ink can be obtained by adding a polybasic acid anhydride to a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid as described in Japanese Patent Publication No. 1-54390. The compound is used as the main component. The solder resist ink obtained by using this compound as a main component has excellent heat resistance and is still widely used today. Further, compositions using a half ester compound of a copolymer of styrene and maleic anhydride described in JP-A-63-11930 and JP-A-63-20564 have been proposed.

However, the ink using the above compound is
There is a problem that tack (adhesiveness) remains during preliminary drying (pre-baking) for removing the solvent. Therefore, there is a problem that the negative film becomes dirty during contact exposure.
Predrying conditions need to be strengthened until tack is completely removed. However, since the ink is hardened by heat and the developability after exposure is deteriorated, there is a limit to the heat treatment temperature, and a method of increasing the treatment time is generally adopted. For this reason,
Prebaking time must be shortened in order to efficiently manufacture printed wiring boards. Furthermore, since this resin has a benzene ring skeleton, it also had the drawbacks of (1) absorption of ultraviolet rays, resulting in low ink sensitivity, and (2) poor electrical characteristics. In order to solve the above problems, JP-A-1-289820 and JP-A-6-138659 are used.
In the publication, there is proposed a resin composition in which an alicyclic epoxy-containing unsaturated compound is added to a poly (meth) acrylic resin.
However, in any case, when used in combination with an epoxy curing agent as a solder resist, there is a problem that the reaction between the carboxyl group and the epoxy group proceeds during pre-baking, resulting in poor developability. JP 2000-7
No. 2814 discloses that after obtaining a resin composition in which an alicyclic epoxy-containing unsaturated compound is added to a poly (meth) acrylic resin, the catalyst used in this synthetic reaction is deactivated by adding hydroperoxide. By the reaction of the carboxyl group and the epoxy group during prebaking (This reaction,
It is considered that a so-called heat fogging phenomenon occurs in the step of drying after applying the resist ink. When this thermal fogging occurs, the unexposed portion that is originally dissolved in the developing solution is not dissolved and a residual film is formed. ) Is suppressed. However, this method has a problem that the number of manufacturing steps is increased.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to suppress the reaction between acid groups and epoxy groups during prebaking, to improve the development failure during development and the film residue, that is, to prevent the occurrence of a heat fogging phenomenon. It is intended to provide a method for producing a curable resin which is suppressed and a composition containing the curable resin obtained by the production method.

[0006]

Means for Solving the Problems As a result of intensive studies to solve such problems, the present inventors have found that they contain a (meth) acrylic acid ester and an unsaturated group and have at least one acid group. When the epoxy group-containing unsaturated compound is reacted with a part of the acid groups of the copolymer obtained from the compound, the amount of the catalyst is reduced, and instead, an oxide of the catalyst is used in combination,
It was found that such a problem can be solved without performing an operation of deactivating the catalyst after the reaction, and the present invention has been completed.

That is, according to the present invention, by using a modified copolymer obtained by adding an epoxy group-containing unsaturated compound to an acid group-containing resin in combination with a catalyst and its oxide, an acid group at the time of pre-baking can be obtained. Suppressed the reaction with the epoxy group, improved the development failure during development, the film residue, that is,
The present invention provides a method for producing a curable resin in which the occurrence of a heat fogging phenomenon is suppressed, and a composition containing the curable resin produced by the method. A first aspect of the present invention is a partial acid group of a copolymer obtained from a (meth) acrylic acid ester (A) and a compound (B) containing an unsaturated group and having at least one acid group. When a modified copolymer (D) having an epoxy group-containing unsaturated compound added thereto is obtained, the addition reaction is carried out in the presence of a catalyst and its oxide. A method for producing a curable resin comprising: A second aspect of the present invention provides a curable resin composition containing a curable resin obtained by the above-mentioned production method, a photopolymerization initiator, a diluting monomer or oligomer as necessary, and an epoxy compound as necessary. .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The modified copolymer (D) used for the production of the curable resin composition of the present invention is a compound (A) containing a (meth) acrylic acid ester (A) and an unsaturated group and having at least one acid group ( A modified copolymer obtained by adding an epoxy group-containing unsaturated compound (C) to some of the acid groups of the copolymer obtained from B) (hereinafter referred to as unsaturated group-containing compound (B)). . Examples of (meth) acrylic acid ester (A) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth).
A hydroxyl group such as (meth) acrylic acid alkyl ester such as acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, or caprocactone-modified 2-hydroxyethyl (meth) acrylate is used. Having (meth) acrylic acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate,
Examples thereof include (meth) acrylates such as methoxytriethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate.

As the unsaturated group-containing compound (B), acrylic acid, methacrylic acid, vinylphenol, and a modified unsaturated monocarboxylic acid having a chain extended between the unsaturated group and the carboxylic acid, for example, β-carboxyethyl (meth ) Acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, lactone modified unsaturated monocarboxylic acid having an ester bond, modified unsaturated monocarboxylic acid having an ether bond Examples include compounds such as carboxylic acids.

As the modified unsaturated monocarboxylic acid, specifically, as a lactone-modified compound of (meth) acrylic acid: CH ₂ ═C (—R ¹ ) CO— [O (CR ² R ³ ) _m CO] _n -OH (1) a terminal hydroxyl group as a lactone-modified product obtained by acid-modified by an acid ^{_{anhydride: CH 2 = C (-R 1}} ) COO-CH 2 CH 2 O [CO (CR 2 CR 3) m O] n COR ⁴ COOH (2) “In the formulas (1) and (2), R ¹ represents a hydrogen atom or a methyl group. M R ² and R ³ each represent a hydrogen atom, a methyl group or an ethyl group. R ⁴ may be different from each other, R ⁴ is a divalent aliphatic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, represents a p-xylylene group, a phenylene group, etc. m represents an integer of 4 to 8 and n represents an integer of 1 to 10. "

As the modified unsaturated monocarboxylic acid having an ether bond, an epoxy compound such as ethylene oxide is added to (meth) acrylic acid, and a hydroxyl group at the molecular end of the adduct is converted into an acid modified product by acid anhydride. general ^{_{formula: CH 2 = C (-R 1}} ) COO - [(CR 2 R 3) m O] n -COR 4 COOH (3) "in the formula, R ^1, .m number representing a hydrogen atom or a methyl group R ² and R ³ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, and may be different from each other, and R ⁴ is a divalent aliphatic saturated or unsaturated group having 1 to 10 carbon atoms. It represents a saturated hydrocarbon group, a divalent alicyclic saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, p-xylylene, a phenylene group, etc. m and n represent an integer of 1 to 10. "
Is mentioned. Alternatively, it may be a compound containing two or more carboxyl groups such as maleic acid in the molecule. Also,
These may be used alone or in combination.

Next, the epoxy group-containing unsaturated compound is added to a part of the acid groups of the copolymer obtained from the above-mentioned (A) and the unsaturated group-containing compound (B) to give the modified copolymer (D ) Is obtained. Epoxy group-containing unsaturated compound (C)
Is a compound having at least one radically polymerizable unsaturated group and an epoxy group in one molecule. Specifically, for example, an alicyclic epoxy group-containing unsaturated compound and glycidyl methacrylate represented by the following structural formula, β
-Aliphatic epoxy group-containing unsaturated compounds such as methyl glycidyl methacrylate and allyl glycidyl ether. Of these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more. In the following general formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ⁸ represents divalent group having 1 to 10 carbon atoms. Is a hydrocarbon group, and m is an integer of 1 to 10.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

The amount of the epoxy group-containing unsaturated compound added is preferably in the range of 5 to 50% by weight with respect to the modified copolymer (D) obtained. If the addition amount is less than 5% by weight, the ultraviolet curability is poor, and the physical properties of the cured coating deteriorate. When it is 50% by weight or more, the storage stability of the resin is deteriorated.

The modified copolymer (D) thus obtained preferably has an acid value of 10 to 150 KOH-mg / g, more preferably 50 to 150 KOH-mg / g. If the acid value is less than 10 KOH-mg / g, it is difficult to remove the uncured film with a dilute aqueous alkaline solution.
When it exceeds 50 KOH-mg / g, there is a problem that the cured film has poor water resistance and electrical properties. The modified copolymer (D) has a weight average molecular weight of 5,000 to 100,000.
It is preferably in the range of. Weight average molecular weight is 5,0
If it is less than 00, (1) the tack-free performance is poor,
(2) There is a problem that the moisture resistance of the coating film after exposure is poor and film slippage occurs during development, resulting in a large deterioration in resolution. On the other hand, if the weight average molecular weight exceeds 100,000, there are problems such as (1) remarkably poor developability and (2) poor storage stability.

The solvent used in the reaction during the production of the curable resin is not particularly limited as long as it can dissolve the raw materials used, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, methanol, ethanol, Alcohols such as 2-propanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether, dibutyl ether and dioxane, ethyl acetate, isobutyl acetate, ethylene glycol monoacetate, propylene glycol monoacetate, dipropylene. Esters such as glycol monoacetate, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol mono Alkyl ethers, butylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dimethyl ether, diethylene glycol dialkyl ethers and other diethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, dimethylformamide, dimethylacetamide Amides such as, carbon tetrachloride, and halogenated hydrocarbons such as chloroform are used. These solvents may be used alone or as a mixture.

Next, the catalyst and its oxide used for producing the curable resin of the present invention will be explained. A catalyst used when the epoxy group-containing unsaturated compound (C) is added to a part of the acid groups of the copolymer obtained from the (meth) acrylic acid (A) and the unsaturated group-containing compound (B). Examples thereof include phosphine compounds such as triphenylphosphine and salts thereof, and the third phosphine typified by triphenylphosphine is preferable. These catalysts may be used alone or in combination. In the present invention, it is essential to use a mixture of a catalyst represented by a third phosphine and its oxide represented by a third phosphine oxide. The total amount of these catalysts and oxides thereof is preferably 0.01 to 10% by weight based on the epoxy group-containing unsaturated compound (C),
More preferably, 0.5 to 3.0% by weight is used. 0.0
If less than 1% by weight, the catalytic effect is low and 10% by weight
If it exceeds the range, the developability of the resist ink may be significantly reduced.

The mixing ratio of the catalyst represented by the third phosphine and the oxide represented by the third phosphine oxide is preferably catalyst / oxide = 9/1 to 5/5 (molar ratio), more preferably Is 8/2 to 7/3 (molar ratio). When the total molar ratio of the catalyst and its oxide is 10,
When the ratio of oxides is 1 or less, the exposure sensitivity of the resist ink is lowered. On the other hand, when the molar ratio of the oxide exceeds 5, the catalytic ability decreases and the production time becomes long, which is not preferable.

Next, the curable resin composition of the present invention will be described. The curable resin composition of the present invention is composed of the curable resin, a photopolymerization initiator, a diluting monomer or oligomer used as necessary, and an epoxy compound used as necessary. Examples of the photopolymerization initiator include benzophenone, acetophenonebenzyl,
Benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite and the like are used alone or in combination. "Irgacure 90" manufactured by Ciba Geigy
A photopolymerization initiator such as 7 ”can also be used. These photopolymerization initiators may also contain a synergist to enhance the conversion of light absorbed energy into polymerization initiating free radicals, such as tertiary amines. When the curable resin composition of the present invention is cured by electron beam irradiation, it is not always necessary to add a photopolymerization initiator. The amount of the photopolymerization initiator added is 0.01 to 10 parts by weight with respect to 100 parts by weight of the curable resin,
Preferably 0.1 to 5 parts by weight, more preferably
0.5 to 3 parts by weight. If less than 0.01 parts by weight,
The curability is not sufficient, and conversely, even if it is used in an amount of 10 parts by weight or more, the curability is not improved, other physical properties of the cured coating film may deteriorate, and the cost increases.

The diluting monomer or oligomer optionally used in the present invention is used from the viewpoint of improving the sensitivity and the characteristics of the curable coating film such as flexibility. The diluting monomer is a compound having a radical-polymerizable double bond represented by an acrylic acid ester or methacrylic acid ester compound, a vinyl aromatic compound such as styrene, and an amide unsaturated compound. Typical acrylic acid ester or methacrylic acid ester is as follows. (Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylic acid esters having a hydroxyl group, such as (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprocactone-modified 2-hydroxyethyl (meth) acrylate,
Methoxydiethylene glycol (meth) acrylate,
Ethoxydiethylene glycol (meth) acrylate,
Isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth)
Acrylate, (meth) acrylates such as methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) acrylates such as methoxypolyethylene glycol # 400- (meth) acrylate, 1,6-hexanedioldi Bifunctional (meth) s such as (meth) acrylate and neopentyl glycol di (meth) acrylate
Trifunctional (meth) acrylic acid esters such as acrylic acid esters and trimethylolpropane tri (meth) acrylate are used. Examples of the oligomer include (meth) acrylic acid esters of polyester polyols, (meth) acrylic acid esters of polyether polyols, adducts of polyepoxy and (meth) acrylic acid, and hydroxyl (hydroxy) via a polyisocyanate to a polyol. Examples thereof include resins in which (meth) acrylate is introduced. The above-mentioned diluted monomers and oligomers can be blended, for example, in the range of preferably 0 to 300 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the curable resin obtained by the above-mentioned production method. When the amount of the polymerizable monomer and oligomer is more than 300 parts by weight, the characteristics of the curable resin of the present invention are reduced.

The epoxy compound, which is one of the constituents used as needed in the curable resin composition of the present invention, increases the inter-crosslink density of the cured coating film in order to improve the electrical properties, weather resistance and chemical resistance. Used. For example, unsaturated group-containing epoxidized resins such as epoxidized polybutadiene and epoxidized butadiene styrene block copolymer can be exemplified. The commercially available products are EPOLIDE PB manufactured by Daicel Chemical Co., Ltd.,
There are ESBS etc. Further, as the alicyclic epoxy resin, for example, Celoxide 202 manufactured by Daicel Chemical Industries, Ltd.
1, EHPE; Mitsui Chemicals, Inc., Epomic VG-3
101; Yuka Shell Epoxy Co., Ltd., E-1031
S: Mitsubishi Gas Chemical Co., Inc., TETRAD-X, TET
RAD-C; Nippon Soda Co., Ltd., EPB-13, EPB
-27 and the like, and examples of the copolymerization type epoxy resin include a copolymer of glycidyl methacrylate and styrene,
CP-50 manufactured by NOF CORPORATION, which is a copolymer of glycidyl methacrylate, styrene and methyl methacrylate
Examples include M, CP-50S, or a copolymer of glycidyl methacrylate and cyclohexylmaleimide.

Other examples include epoxidized resins having a special structure. In addition, novolak type epoxy resin (for example, phenol, cresol, halogenated phenol, and alkylphenol, etc. obtained by reacting novolaks and epichlorohydrin and / or methyl epichlorohydrin obtained by reacting formaldehyde with formaldehyde under an acidic catalyst. The commercially available products include EOCN-103, E manufactured by Nippon Kayaku Co., Ltd.
OCN-104S, EOCN-1020, EOCN-1
027, EPPN-201, BREN-S: Dow Chemical Co., DEN-431, DEN-439: Dainippon Ink and Chemicals, Inc., N-73, VH-4150, etc.), bisphenol type epoxy resin (For example, those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin, or by reacting a diglycidyl ether of bisphenol A with a condensate of the above bisphenols and epichlorohydrin The obtained products are listed as the commercially available products, manufactured by Yuka Shell Co., Ltd., Epicoat 1004, Epicoat 100.
2; DER-330, DER-337 manufactured by Dow Chemical Co.
Etc.), trichlorophenol methane, triscresol methane, and the like, and / or those obtained by reacting with epichlorohydrin and / or methylepichlorohydrin. As commercially available products, Nippon Kayaku Co., Ltd. EPPN-501, EPPN-
502), tris (2,3-epoxypropyl) isocyanurate, biphenyl diglycidyl ether, etc. can also be used. These epoxy resins may be used alone or in combination. These epoxy compounds are, for example, curable resin 100 obtained by the above-mentioned manufacturing method.
It is preferably added in an amount of 0 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on parts by weight. When the amount of the epoxy compound is more than 100 parts by weight, the characteristics of the curable resin of the present invention are reduced.

The curable resin composition of the present invention may further contain a thermal polymerization inhibitor, a surfactant, a light absorber, a thixotropic agent, a dye and a pigment as other additives as required. Further, a thermoplastic resin, a thermosetting resin or the like can be blended. The composition of the present invention can be cured by applying it as a thin film on a substrate. As a method for forming a thin film, spraying, brushing, roll coating, curtain coating, electrodeposition coating, electrostatic coating, etc. are used.

When the curable resin composition of the present invention is used as a component of a liquid resist or a dry film, the curable resin composition can be applied onto a substrate and then cured by light. "Light" is a high-pressure mercury lamp,
Light such as ultraviolet rays, electron beams and laser beams can be used. When it is used as one component of a liquid resist or a dry film, it can be cured by heat. The curing conditions are 100 to 200 ° C. and 1 to 9
It can be performed under the condition of 0 minutes. The curing is preferably carried out in an inert gas atmosphere, but it can also be carried out in an air atmosphere.

The curable resin and the curable resin composition according to the present invention are used in various coating fields such as ink, plastic paint, paper printing, film coating, and furniture coating, FRP, lining, and insulating varnish and insulating sheet in the electronics field. It can be applied to many industrial fields such as laminated plates, printed boards, resist inks, pigment resist inks for color filters, and semiconductor encapsulants.

[0027]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. The evaluation test was conducted by the following method. Preparation of ink composition for evaluation: 100 parts by weight of resin solutions A1 to 9 (solid content), 20 parts by weight of trimethylolpropane triacrylate, and epoxy equivalent of cresol novolac type epoxy resin (Epicoat manufactured by Yuka Shell Epoxy Co., Ltd.). 1
80S70) 20 parts by weight, benzyl methyl ketal 7 parts by weight, diethyl thioxanthone 2 parts by weight, phthalocyanine green 1.5 parts by weight, silica 5 parts by weight, barium sulfate 20 parts by weight, dicyandiamide 5 parts by weight, and then three rolls. And kneaded to obtain a viscous ink composition. The ink obtained above was applied on a patterned substrate using a bar coater to a thickness of 20 μm. 1. Developability test: The coating film obtained above was dried for 80, 100, 140 minutes by a blast dryer at 80 ° C. The dried coating film was developed with a 1% sodium carbonate aqueous solution, and the heat fogging property was evaluated based on the time (seconds) required for the development. 2. Exposure sensitivity measurement: The coating film obtained above was dried for 20 minutes by a blast dryer at 80 ° C. Then, a negative film (21-step tablet manufactured by Stofer Co., Ltd., the higher the number of steps, the higher the sensitivity) was brought into close contact with the film and irradiated with a light amount of 800 mJ / cm ² . Further, it was developed with a 1% sodium carbonate aqueous solution, and the obtained coating film was cured in a 150 ° C. blower oven for 30 minutes.

(Example 1) 300 g of dipropylene glycol monomethyl ether (MFDG manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube. After heating to 95 ° C., 151 g of methacrylic acid (1.76)
Mol), 110 g of methyl methacrylate (1.1 mol), 200 g of MFDG and t-butylperoxy 2
-Ethyl hexanoate (Perbutyl O manufactured by NOF CORPORATION) 1
Both 6.6 g were added dropwise over 3 hours. After dropping, the mixture was aged for 4 hours to synthesize a trunk polymer having a carboxyl group. Next, 239 g (1.3 mol) of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A-200 manufactured by Daicel Chemical Industries, Ltd.), triphenylphosphine (hereinafter abbreviated as TPP) and triphenylphosphine were added to the above trunk polymer solution. Oxide (hereinafter abbreviated as TPPO) is TPP / TPPO
= 9/1 molar ratio and total cyclomer A-20
1 part by weight of 0 and 1.0 g of methylhydroquinone were added and reacted at 110 ° C. for 10 hours. Reaction is air
/ It was performed under a mixed atmosphere of nitrogen. This gives an acid value of 50
A curable resin solution (A-1) having KOH-mg / g, double bond equivalent (resin weight per 1 mol of unsaturated group) 381 and weight average molecular weight of 11,000 was obtained.

100 parts by weight of the curable resin solution A-1, 25 parts by weight of trimethylolpropane triacrylate, 15 parts by weight of a bisphenol A type epoxy resin (YD-128 manufactured by Toto Kasei Co., Ltd.) having an epoxy equivalent of 220, and 2 parts by weight of phthalocyanine green. Parts, "Irgacure 907" manufactured by Ciba-Geigy Co., Ltd. as an initiator, and then kneaded with three rolls,
A viscous ink composition was obtained. The developability of this ink composition was evaluated, and the results are shown in Table 1.

(Example 2) The molar ratio of TPP / TPPO was 8/2.
A reaction was performed in the same manner as in Example 1 except that the above was used to obtain a curable resin solution (A-2). An ink composition having the same composition as in Example 1 was prepared using the curable resin solution (A-2), and the developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1. (Example 3) A reaction was performed in the same manner as in Example 1 except that the molar ratio of TPP / TPPO was changed to 7/3, and then 1 g of dimethylbenzylamine was added to obtain a curable resin solution (A-3). It was An ink composition having the same composition as in Example 1 was prepared using the curable resin solution (A-3), and the developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1. (Example 4) The reaction was performed in the same manner as in Example 1 except that the molar ratio of TPP / TPPO was changed to 5/5, and then hydrogen peroxide solution (3
0.8% of 0%) was added to obtain a curable resin solution (A-4). An ink composition having the same composition as in Example 1 was prepared using the curable resin solution (A-4), and the developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1.

(Example 5) 300 g of dipropylene glycol monomethyl ether (MFDG manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube.
After heating to 95 ° C., 152 g (1.75 mol) of methacrylic acid, 162 g (1.62 mol) of methyl methacrylate, 200 g of MFDG and t-butylperoxy 2
-Ethyl hexanoate (Perbutyl O manufactured by NOF CORPORATION) 2
0 g was added dropwise over 3 hours. After dropping, the mixture was aged for 4 hours to synthesize a trunk polymer having a carboxyl group. next,
186 g (1.3 mol) of glycidyl methacrylate (Blenmer G manufactured by NOF CORPORATION) and TPP were added to the above trunk polymer solution.
The total molar ratio of TPPO and TPPO is 7/3, and the total amount is 1 part by weight based on glycidyl methacrylate.
0 g was added and reacted at 100 ° C. for 10 hours. The reaction is
It was performed under a mixed atmosphere of air / nitrogen. This gives an acid value of 50 KOH-mg / g, double bond equivalent (unsaturated group 1 mol
Resin weight per unit) 381, weight average molecular weight 10,500
To obtain a curable resin solution (A-5). An ink composition having the same composition as in Example 1 was prepared using the curable resin solution (A-5), and the developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1.

(Comparative Example 1) The molar ratio of TPP / TPPO was 10 /
A reaction was carried out in the same manner as in Example 1 except that the value was 0 to obtain a curable resin solution (A-6). Using the curable resin solution (A-6), an ink composition having the same composition as in Example 1 was prepared,
The developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1. (Comparative Example 2) The reaction was carried out in the same manner as in Example 1 except that the molar ratio of TPP / TPPO was changed to 10/0 and the amount of triphenylphosphine used was changed to 4/5 of that of Comparative Example 1. Oxidation deactivation of triphenylphosphine was omitted and a curable resin solution (A-7) was obtained. Using the curable resin solution (A-7), an ink composition having the same composition as in Example 1 was prepared,
The developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1. (Comparative Example 3) The reaction was performed in the same manner as in Example 1 except that the molar ratio of TPP / TPPO was 10/0 and the amount of triphenylphosphine used was 1/2 the amount of Comparative Example 1. Oxidation deactivation of triphenylphosphine was omitted and a curable resin solution (A-8) was obtained. Using the curable resin solution (A-8), an ink composition having the same composition as in Example 1 was prepared,
The developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1. (Comparative Example 4) The reaction was carried out in the same manner as in Example 5 except that the molar ratio of TPP / TPPO was changed to 10/0. Oxidative deactivation of triphenylphosphine after completion of the reaction was omitted, and the curable resin solution (A -9) was obtained. Using a curable resin solution (A-9),
An ink composition having the same formulation as in Example 1 was prepared, and the developability was evaluated under the same conditions as in Example 1. The results are shown in Table 1.

[0033]

[Table 1]

In Table 1, the "reaction time ratio" was calculated by the reaction time when the reaction time of the system having a molar ratio of 10/0 was set to 1 and the ratio of TPP / TPPO was changed. The time required until the end of the reaction is the above-mentioned "Cyclomer A20".
It was measured by confirming that the concentration of "0" was 1% or less by gas chromatography. When the reaction time ratio is 1,
It is about 10 hours. It is judged that the one in which the change in the developing speed with time is small and the reaction time is not much different from the conventional one (a system of TPP / TPPO = 10/0) and the exposure sensitivity is large is preferable. For example, when comparing Example 2 with Comparative Example 2, since TPPO was added to Example 2, the change in development rate with time was small and the sensitivity was lowered, even though the amount of TPP was reduced. There is no such thing. On the other hand, Comparative Examples 2 and 3
As shown in (3), the exposure sensitivity is lowered and the reaction time is delayed by simply reducing the amount of TPP. Incidentally, in any of the above-mentioned Examples and Comparative Examples
The deactivating operation by oxidation of TPP as described in 0-72814 is not performed.

[0035]

As is clear from these results, it was found that the inks of Examples had excellent thermal stability in the presence of epoxy compounds.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA04 AB11 AB15 AC01 AD01                       BC13 BC31 BC53 BC81 BC84                       CA00 CB13 CB14 CB42 EA08                 4J027 AE04 CC03 CC05 CD06                 4J100 AJ01Q AL02P HA11 HC39                       JA38 JA46

Claims (6)

[Claims] 1. An epoxy compound as a part of an acid group of a copolymer obtained from a (meth) acrylic acid ester (A) and a compound (B) containing an unsaturated group and having at least one acid group. When the modified copolymer (D) to which the group-containing unsaturated compound (C) is added is obtained, the addition reaction is carried out in the presence of a catalyst and its oxide. Method for producing curable resin. 2. The method for producing a curable resin according to claim 1, wherein the catalyst is a third phosphine. 3. The method for producing a curable resin according to claim 1, wherein the acid value of the curable resin is in the range of 10 to 150. 4. The epoxy group-containing unsaturated compound is 3,4-
The method for producing a curable resin according to claim 1, which is an epoxycyclohexylmethyl (meth) acrylate. 5. A curable resin obtained by the method according to any one of claims 1 to 4, a photopolymerization initiator, a diluting monomer or oligomer if necessary, and an epoxy compound as necessary. Curable resin composition. 6. The curable resin composition according to claim 5, which is used as one component of a liquid resist or a dry film and is photocurable or thermosetting.